Process for the manufacture of halogenated anthraquinones



pp No Patented Sept. 30, 1930' ARNOLD snnrnnnnsonj WILLIAM WYNDHAM TATUM, menses inILLs BUNB'U'BY,

OF MANCfiE$TER,'ENGLAND, ASSIGNORS T0 BRITISH nYEsTUrrsconroaA'r-IoN LIM- v 'IV'IED, or maacnssmag; enemas rzaoonss r03 THE Manor-Aswan or HALOGENATED aniuiriaournonns p In obtaining derivativesoflAc-fdianiino-anthraquinone, e. ithas been the practice to synthesize the 1.4;- diamino-anthraquinone by starting with 1.- amino-anthraquinone, acetylating, iiitr'ating, and hydrolyzing the l nitro-l-acetylamino anthraquinone thus produced to 1-nitrolamino -anthra quinone, and then reducing the nitro group. The 1.4-.diamino anthraquinone thus obtained has been reacted upon in;

known manner to forin the required deriva} tives. l V

Wenow findthat if a leuco 1 2 e-diamih anthraquinone is treated with benzoylating, halogenating and other agents in the presence of an oxidizing solvent,,thereis formed the corresponding derivative of l a-diarnino-an thraquinone and not thefderivative of the leuco body. Both oxidation and for instance ben 'zoylation or one operation;

In this process nitro bodies such as nitrobenzenefo'r' nitrotoluene are uit able oxidizing solvents. Other oxidizing solventsor agents may be used in addition or substitution. The process is. advantageous as two reactionsare performed in a single step. It provides a simple and direct synthesis of substances which are important dyestufii i i-i ter1mediates,- with isolation of theend product on y. The process is especially advantageous in view of recent developments in theart. In a copending application of one of us (Tatum;

. Ser. No. 87,447) there is disclosed a new process for the productionof'leuco '1 :f t-diiaminoanthraquinones from 1 -dihydroxy or amino-hydroxy anthraquinones. The so produced leuco anthraquinones are converted into valuable dyestufi' intermediates by the present process in-a simple and advantageous manner. The combination of these two processes provides a means of converting 1: -di: hydroxy or amino-hydroxyanthraquinone into 1: l-diamino-anthraquinone derivatives in a satisfactory and eflicient manner.

However the present invention is equally advantageous when leuco compounds pre pared by other methods are used. The benefits flowing from oxldizing and benzoylating g. the dibe'nzoyl derivative? 7 7 170 parts of 'suspensionof lOOparts of Ieu'c'oiA-diamihohalogenation take place, in

Drawing. Kpplieation filed Iteliruar-y T6 1926 Serial No. 87,433, and in Great Britain January 11, 1926,

or halogenating in one step are independent of the source of the leuco compound. 7 In the present invention the leuco 1 :4-' di'-' amino-anthraquinone is reacted upon; inthe presence of an oxidizing solvent, such as nitrobenzene, and the end product isolated directly therefrom by suitable means.

The following examples will serve to illustrate the nature of the invention; but the scope of the invention is not confined to theexampics. The parts given are by iweight. Eaam le 1. Direat camersion of; Zeaca 1.4-diamino-amhmqainoae t0 LL-dz'btmzoyl-dz'amz'na-anthraquinone benz'oyl chloride are added to a anthraquinone in 600 parts ofnitrobenzene and the whole heated to 110ll0 C. The brown color of the leuco diaminle soon changes to redwith evolution'of hydrochloric acid on cooling thepure 1.4dibenz oyl-diaminoanthraquinone comes out of solutionin the nnoooom- E'wa'mple 2.1 Preparation of anthraq'u'inoneone are stirred at 35-50 ant ant-hraquinone-l.4-dioxamie acid which crystallizes out may be filtered off and dried. The product may be purified if desired by dissolving it in hot sodium carbonate or ammonia solution, filtering from any insoluble matter, and reprecipitating with acid. This product probably has the formula:

(I) NH.CO.COOH

NH.G0.000H

This acid forms a brown powder soluble in caustic soda solution with a red color. On boiling such a solution the oxalic residue is hydrolyzed oil" and pure 1.4-diainino-anthraquinone is obtained.

Ewample 3. Direct conversion of leuco 1.4-

diam-z'ao-ant/zmguin0nc to 2.3-dichlr0 1.4-dz'amz'n0-anthmguinonc 100 parts of leuco 1.4-diamino-anthraquin- C. with 600 parts of nitrobenzene and treated at this temperature with a current of chlorine gas. Ifdesired a small quantity of a catalyst such'as iodine or sulphur may be added. Oxidation and chlorination take place apparently simultaneously, and the liberated hydrochloric acid combines with the 2.3-dich1or l/i-diaminoanthraquinone to form 2.3-dichlor 1.4-di.ami

no-anthraquinone-hydrochloride. We have found it of importance in securing good yields to stop the current of chlorine as soon as the reaction has proceeded far enough, which is the case when a drop of the melt imparts no purple tinge to boiling water. When this stage has been reached the precipitate is filtered off, neutralized with alcoholic ammonia, and dried. Pure 2.3-dichlor 1.4-diaminoanthraquinone is thereby obtained in good yield directly from leuco 1. l-diamino-anthraqulnone. The compound probably has the formula:

0 NH; I

( l l IHg Example 4. Direct conversion of leuco 1.4- dzamzno-anthmqumonc to 1-amin0-4-benzog l-ammo-anthmgm'none To parts of leuco 1.4.diamino anthraquinone dissolved in 80 parts of nitrobenzene and raised to 160180 0., add 12 parts of benzoic anhydride dissolved inparts of nitro-benzene. Maintain at 160 C. with stirring for twohours. Cool,- filter, and remove the solvent by washing with alcohol or by steam distillation. Upon drying the filter cake, pure l-amino-t-benzoylaminoanthraquinone is obtained in excellent yield.

The compound probably has the formula:

NH.CO.CnH

From the filtrate a recovery of benzoic acid may be made if desired.

We claim v 1. In the manufacture of halogenated 1 4- diamino-anthraquinones directly from leuco 1 4 diamino anthraquinones, the process which comprises treating a leuco 1 4c-diamino-anthraquinone with a halogenating agent in the presence of a solvent having oxidizing properties.

2. In the manufacture of halogenated 1: 1- diamino-anthraquinones directly from leuco 1: 4 diamino anthraquinones, the process which comprises treating a leuco 1 -diamino-anthraquinone with a halogenating agent in the presence of a liquid aromatic nitro compound as an oxidizing solvent.

3. In the manufacture of halogenatedl 4- diamino-anthraquinones, directly from leuco 1 4 4 diamino anthraquinones, the process which comprises treating a leuco 1 4.--diamino-anthraquinone with a halogenating agent in the presence of nitrobenzene.

4. In the manufacture of chlorinated 1 4- diamino-anthraquinones directly from 1 4tdiamino-anthraquinones the process which comprises treating leuco 1 4-diamino-anthraquinone with chlorine in the presence of a liquid aromatic nitro compound as an oxidizing solvent.

5. In the manufacture of chlorinated 1: 4- diamino-anthraquinones directly from leuco 1: 4L diamino anthraquinones the process which comprises treating leuco 1 4-diaminoanthraquinone with chlorine in the presence of nitrobenzene.

In testimony whereof we have hereunto afiixed our signatures.

ARNOLD SHEPHERDSON. WILLIAM WYNDHAM TATUM. HUGH MILLS BUNBURY. 

